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Publication numberUS6025289 A
Publication typeGrant
Application numberUS 08/984,938
Publication dateFeb 15, 2000
Filing dateDec 4, 1997
Priority dateFeb 5, 1996
Fee statusPaid
Also published asCA2244262A1, CA2244262C, CN1210565A, CN1291073C, CN1891866A, CN100593591C, DE69704483D1, DE69704483T2, EP0879305A1, EP0879305B1, US5718760, US6200917, WO1997028297A1
Publication number08984938, 984938, US 6025289 A, US 6025289A, US-A-6025289, US6025289 A, US6025289A
InventorsCalvin H. Carter, Valeri F. Tsvetkov, Robert C. Glass
Original AssigneeCree Research, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Single crystals doped with nitrogen and aluminum; synthetic gemstones having extraordinary toughness and hardness, and brilliance meeting or exceeding that of diamond
US 6025289 A
Abstract
Large single crystals of silicon carbide are grown in a furnace sublimation system. The crystals are grown with compensating levels of p-type and n-type dopants (i.e., roughly equal levels of the two dopants) in order to produce a crystal that is essentially colorless. The crystal may be cut and fashioned into synthetic gemstones having extraordinary toughness and hardness, and a brilliance meeting or exceeding that of diamond.
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Claims(10)
That which is claimed:
1. A colorless single crystal of silicon carbide having compensated levels of nitrogen as an n-type dopant and aluminum as a p-type dopant; said nitrogen dopant and said aluminum dopant each being present in the crystal at a concentration of between about 11016 cm-3 and 11018 cm-3 ; and with the concentration of aluminum dopant atoms being in the range of about one to five times that of nitrogen dopant atoms.
2. A colorless single crystal of silicon carbide as claimed in claim 1 wherein each dopant type is present in the crystal at a concentration of between about 11017 cm-3 and 51017 cm-3.
3. A colorless single crystal of silicon carbide as claimed in claim 1 wherein the concentration of aluminum atoms is between about one and two times the concentration of nitrogen atoms.
4. A colorless single crystal of silicon carbide as claimed in claim 1 wherein nitrogen atoms are present at a concentration dictated by background levels of nitrogen.
5. A colorless single crystal of silicon carbide as claimed in claim 1 wherein the polytype of the silicon carbide single crystal is selected from the group consisting of 2H, 6H, 4H, 8H, 15R and 3C.
6. A colorless single crystal of silicon carbide having compensated levels of nitrogen as an n-type dopant and boron as a p-type dopant; said nitrogen dopant and said boron dopant each being present in the crystal at a concentration of between about 11016 cm-3 and 11017 cm-3.
7. A colorless single crystal of silicon carbide as claimed in claim 6 wherein the concentration of boron atoms is between about one and two times the concentration of nitrogen atoms.
8. A colorless single crystal of silicon carbide as claimed in claim 6 wherein nitrogen atoms are present at a concentration dictated by background levels of nitrogen.
9. A colorless single crystal of silicon carbide as claimed in claim 6 wherein the polytype of the silicon carbide single crystal is selected from the group consisting of 2H, 6H, 4H, 8H, 15R and 3C.
10. A colorless single crystal of silicon carbide as claimed in claim 6 wherein the concentration of boron atoms and nitrogen atoms are substantially equal.
Description

This application is a division of application Ser. No. 08/596,526, filed Feb. 5, 1996, now U.S. Pat. No. 5,718,760.

FIELD OF THE INVENTION

The invention relates to the growth of silicon carbide crystals. More particularly, the invention relates to the growth of transparent, monocrystalline, colorless silicon carbide crystals. Because of their durability and other advantageous physical and crystal properties, these crystals may be cut and fashioned into finished gemstones having the fire and brilliance of diamond.

BACKGROUND OF THE INVENTION

Silicon carbide (SiC) is rarely found in nature. It has, however, been manufactured for more than eighty years, in crystalline form, for abrasive products. Silicon carbide crystals found in nature and in abrasive products are generally black and not translucent because they contain substantial levels of impurity atoms.

Because of the theoretically quite favorable electronic properties of silicon carbide, significant development activities were initiated during the 1960s and 1970s with the objective of growing large (bulk) crystals of low impurity silicon carbide for use in the production of semiconductor devices. These efforts finally resulted in the commercial availability of relatively low impurity, translucent silicon carbide crystals. These silicon carbide crystals are fabricated and marketed as very thin, green, amber or blue (175 μm-400 μm) slices useful for semiconductor devices.

Recently, it has been discovered that relatively low impurity, translucent, single crystal silicon carbide may be grown with a desired color and thereafter cut and fashioned into synthetic gemstones. These gemstones have extraordinary hardness, toughness, chemical and thermal stability, and a high refractive index that produces unparalleled brilliance. The single crystals from which the gemstones are produced have been grown by sublimation according to techniques of the type described in U.S. Pat. No. Re. 34,061.

Silicon carbide crystals can be grown in a wide range of colors (including green, blue, red, purple. yellow, amber and black) and shades within each color by the appropriate selection of dopants (e.g., nitrogen and aluminum) and by varying the net doping densities (concentrations). Because of its wide bandgap, undoped ("intrinsic") silicon carbide crystals in the hexagonal or rhombohedral forms are inherently colorless. Thus, silicon carbide crystals offer the potential to be cut and fashioned into gemstones of many various appearances, including that of diamond.

Although the colored crystals have proven relatively easy to produce, problems have been encountered in creating the exceedingly impurity-free sublimation system environment necessary for growing undoped, colorless silicon carbide. Because colorless silicon carbide gemstones have an extraordinary appeal, there is a need for a more cost effective and reliable process for growing large single crystals of silicon carbide in colorless form.

SUMMARY OF THE INVENTION

The present invention, in one broad aspect, is the discovery that large, transparent, colorless silicon carbide crystals may be grown in a sublimation system where compensating levels of n-type and p-type dopants are introduced into the crystals's lattice structure. The compensated levels of p-type and n-type dopants (i.e., roughly equal levels of the two dopants) serve to produce a colorless crystal by canceling each other in terms of the production of color centers in the crystal. The compensation is best carried out at low carrier levels. For example, the preferred n-type dopant, nitrogen, may be introduced into the lattice only at those low levels dictated by "background" atmospheric nitrogen present in the sublimation system. A like amount of p-type dopant, e.g., aluminum, may be introduced via the sublimation powder or gas at a level sufficient to compensate for the background level of nitrogen. Thus, in one aspect, the present invention may be described as a colorless single crystal of silicon carbide grown with compensated levels of n-type and p-type dopants. These crystals may be cut and fashioned into brilliant colorless synthetic gemstones.

In another aspect, the invention may be defined as a method of producing a colorless single crystal of silicon carbide comprising the step of growing the single crystal of silicon carbide by a sublimation technique wherein compensated levels of p-type and n-type dopants are introduced into the crystal lattice structure.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood at the outset of the description which follows that persons of skill in the appropriate arts may modify the invention as herein described while still achieving the favorable results of this invention. Accordingly, the description which follows is to be understood as being a broad, teaching disclosure directed to persons of skill in the appropriate arts, and not as limited upon the present invention.

Additionally, a number of the definitions, techniques and other aspects in the field of natural and synthetic gems and gemstones are well known to those of ordinary skill in this art. Relevant background and related information can be found, for example, in Volume 7 of the McGraw-Hill Encyclopedia of Science & Technology, 7th Ed. (1992) at pages 651-659. It will be understood, of course, that this source is exemplary of the general knowledge in this art, rather than any limitation of the present invention.

In a preferred manner of practicing the invention, the growth of large, colorless single crystals of silicon carbide is achieved by introducing a polished monocrystalline seed crystal of silicon carbide of a desired polytype into the furnace of a sublimation system along with silicon and carbon containing source gas or powder (source material). The source material is heated to a temperature that causes the source material to create a vapor flux that deposits vaporized Si, Si2 C, and SiC2 to the growth surface of the seed crystal. The reproducible growth of a single selected polytype on the seed crystal is achieved by maintaining a constant flux of Si, Si2 C and SiC2, and controlling the thermal gradient between the source material and the seed crystal. The growth procedure described above is set forth in more detail in U.S. Pat. No. Re. 34,861, the teachings of which are incorporated entirely herein by reference.

During the growth process of the present invention, roughly equal amounts of p-type and n-type dopants are maintained in the atmosphere of the sublimation furnace so that compensated levels of these two dopant types are introduced into the crystal lattice structure. In one preferred embodiment, the n-type dopant is nitrogen. The nitrogen source is the nitrogen present in the furnace atmosphere at "background" levels. Therefore, according to this embodiment, a p-type dopant, preferably aluminum, is added to the source powder in an appropriate amount so that the nitrogen and aluminum are incorporated into the crystal lattice structure in compensated amounts. In this regard, "compensated," "compensated amount," "compensated level," and like terms, are used to refer to those roughly equal levels of p-type and n-type dopant atoms incorporated into the silicon carbide crystal lattice structure whereby the crystal is rendered essentially colorless.

In this regard, the terms "compensation" or "compensated" are also used in describing the electronic properties of a crystal, and likewise describes a semiconductor material that contains (frequently intentionally) both p and n-type dopants, including material in which one or the other predominates; e.g. a "compensated p-type material." Also, some uses refer to material in which p or n predominate as being "overcompensated" rather than simply "compensated." Thus, the terms "compensated" and "overcompensated" are familiar to those of ordinary skill in the semiconductor field.

It has been found desirable to compensate p-type and n-type dopants at low carrier levels. Thus, prior to initiating the sublimation growth process, the background level of atmospheric nitrogen in the furnace is desirably reduced to a relatively low level, for example, a level that will generally create an n-type dopant level in the crystal lattice on the order of about 11016 to 11018 atoms/cubic centimeter (cm-3) with a more preferred range being between about 11017 cm-3 5 to 1017 cm-3. Reducing the level of atmospheric nitrogen in the furnace can be achieved by methods known in the art, typically, by backfilling with an inert gas such as argon, following by evacuating the furnace to very low pressure.

The compensated level of the p-type dopant is not absolutely critical provided it produces a crystal having sufficient colorless properties for the intended end use. Thus, broadly stated, the invention encompasses compensation that meets this goal, whether the dopant density is greater for the p-type or n-type dopant. It has been found desirable, however, especially where the n-type dopant is nitrogen and the p-type dopant is aluminum, to have a greater density of aluminum atoms in the crystal lattice. Thus, in a preferred manner of practicing the invention, the level of aluminum atoms is in the range of one to five times that of the nitrogen atoms, with a more preferred range being one to two times.

The reasons for a somewhat greater density of p-type S aluminum atoms are two-fold. First, p-type aluminum doping alone tends to impart a blue color to silicon carbide crystals, while n-type nitrogen doping alone tends to impart a green or amber color. Because colorless brilliance for gemstone applications is desired, a slight blue tint is preferable to a slight green or amber tint. Generally speaking, the preference arises from the aesthetic viewpoint that a blue tint is less detrimental than some other tint and, in some cases, is deemed desirable. The second reason for erring on the side of aluminum overcompensation is that aluminum is a deeper level dopant than nitrogen. Thus, at room temperature, the crystal will contain fewer active carriers due to an overcompensation of nitrogen. Because active carrier concentration is directly linked to the creation of color centers within the crystal, an overcompensation of aluminum is more likely to reduce the color of the crystal than will an overcompensation of nitrogen.

It will be appreciated that other dopants may be used, and that the dopants may be used at other densities. For example, the p-type dopant may be boron or beryllium, or other Group I, II or III elements. Similarly, other Group V elements may be used as n-type dopants in silicon carbide.

The present invention may be utilized to grow colorless crystals of different polytypes. In this regard, silicon carbide is a complex material system that forms more than 150 different polytypes, each having different physical and electronic properties. The different polytypes can be classified in three basic terms: cubic, rhombohedral and hexagonal. Both the rhombohedral and hexagonal forms can occur in a number of different atomic arrangements that vary according to atomic stacking sequence. According to the invention, the preferred polytypes are 2H, 6H, 4H, 8H, 15R and 3C.

Large, colorless single crystals of silicon carbide grown by the techniques described above are ideally suited for use as gemstone materials. The colorless single crystals, if large enough, are first cut into a number of smaller pieces that serve as the rough gemstone material. The rough gemstones thereafter may be fashioned into finished gemstones by utilizing equipment currently employed in the art for fashioning diamonds and natural colored gemstones. Preferably, the silicon carbide gemstones of the invention are fashioned with precision diamond cuts to take advantage of the extraordinarily high refractive index of the silicon carbide material.

As noted earlier, those techniques required to turn an appropriate material into a final gemstone are generally well understood, and can be applied to the silicon carbide material of the present invention without undue experimentation.

Although the invention has been described in connection with certain embodiments, it will be appreciated that modifications may be made without departing from the true spirit and scope of the invention.

Patent Citations
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Non-Patent Citations
Reference
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US6706114May 21, 2001Mar 16, 2004Cree, Inc.Methods of fabricating silicon carbide crystals
US6749685 *Aug 16, 2001Jun 15, 2004Cree, Inc.Silicon carbide sublimation systems and associated methods
US6875376 *Jul 25, 2002Apr 5, 2005Murata Manufacturing Co., Ltd.Voltage non-linear resistor, method for manufacturing the same, and varistor using the same
US7135072Jan 14, 2004Nov 14, 2006Cree, Inc.Methods of fabricating silicon carbide crystals
US7192482Aug 10, 2004Mar 20, 2007Cree, Inc.Seed and seedholder combinations for high quality growth of large silicon carbide single crystals
US7255743Aug 19, 2003Aug 14, 2007International Research & Recovery CorporationMethod of making synthetic gems comprising elements recovered from remains of a species of the kingdom animalia
US7294324Jun 8, 2005Nov 13, 2007Cree, Inc.A high quality single crystal wafer of SiC having a diameter of at least 3 inches and at least one continuous square inch of surface area that has a basal plane dislocation density less than 500 cm; wafers used as precursors for semiconductor purposes, and for seeded sublimation crystal growth
US7338822May 6, 2004Mar 4, 2008Cree, Inc.LED fabrication via ion implant isolation
US7364617Feb 5, 2007Apr 29, 2008Cree, Inc.Seed and seedholder combinations for high quality growth of large silicon carbide single crystals
US7422634Apr 7, 2005Sep 9, 2008Cree, Inc.Three inch silicon carbide wafer with low warp, bow, and TTV
US7501022Oct 4, 2006Mar 10, 2009Cree, Inc.Methods of fabricating silicon carbide crystals
US7553373May 18, 2006Jun 30, 2009Bridgestone CorporationSilicon carbide single crystal and production thereof
US7592634Jun 16, 2005Sep 22, 2009Cree, Inc.LED fabrication via ion implant isolation
US7943406Dec 4, 2008May 17, 2011Cree, Inc.LED fabrication via ion implant isolation
US7943954Jul 22, 2009May 17, 2011Cree, Inc.LED fabrication via ion implant isolation
US8013343Oct 27, 2005Sep 6, 2011Sumitomo Electric Industries, Ltd.Silicon carbide single crystal, silicon carbide substrate and manufacturing method for silicon carbide single crystal
US8772757Feb 13, 2008Jul 8, 2014Cree, Inc.Deep ultraviolet light emitting devices and methods of fabricating deep ultraviolet light emitting devices
EP1652973A1 *Oct 27, 2005May 3, 2006Sixon Ltd.Silicon carbide single crystal, silicon carbide substrate and manufacturing method for silicon carbide single crystal
Classifications
U.S. Classification501/86, 501/88, 117/951, 252/62.30C
International ClassificationC30B23/00, C30B29/36
Cooperative ClassificationC30B23/00
European ClassificationC30B23/00
Legal Events
DateCodeEventDescription
Jul 13, 2011FPAYFee payment
Year of fee payment: 12
Jul 20, 2007FPAYFee payment
Year of fee payment: 8
Jul 21, 2003FPAYFee payment
Year of fee payment: 4
May 17, 2000ASAssignment
Owner name: CREE, INC., NORTH CAROLINA
Free format text: CHANGE OF NAME;ASSIGNOR:CREE RESEARCH, INC.;REEL/FRAME:010832/0545
Effective date: 19991201
Owner name: CREE, INC. 4600 SILICON DRIVE DURHAM NORTH CAROLIN